US4944813A - Process for phosphating metal surfaces - Google Patents
Process for phosphating metal surfaces Download PDFInfo
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- US4944813A US4944813A US07/297,155 US29715589A US4944813A US 4944813 A US4944813 A US 4944813A US 29715589 A US29715589 A US 29715589A US 4944813 A US4944813 A US 4944813A
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- ions
- process according
- phosphated
- metal
- zinc
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- 238000000034 method Methods 0.000 title claims abstract description 37
- 230000008569 process Effects 0.000 title claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 34
- 239000002184 metal Substances 0.000 title claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 29
- 239000011701 zinc Substances 0.000 claims abstract description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005482 strain hardening Methods 0.000 claims abstract description 12
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 8
- 150000002828 nitro derivatives Chemical class 0.000 claims abstract description 7
- 230000004913 activation Effects 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- -1 Ca2+ ions Chemical class 0.000 claims description 21
- 229910019142 PO4 Inorganic materials 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 3
- 229910000640 Fe alloy Inorganic materials 0.000 claims 6
- 229910001297 Zn alloy Inorganic materials 0.000 claims 6
- HENMSNJYDGNBMU-UHFFFAOYSA-M calcium;zinc;octadecanoate Chemical compound [Ca+2].[Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O HENMSNJYDGNBMU-UHFFFAOYSA-M 0.000 claims 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052725 zinc Inorganic materials 0.000 abstract description 9
- 229910052742 iron Inorganic materials 0.000 abstract description 6
- 239000000956 alloy Substances 0.000 abstract description 5
- 229910045601 alloy Inorganic materials 0.000 abstract description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract 2
- 239000000344 soap Substances 0.000 description 11
- 235000021317 phosphate Nutrition 0.000 description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 8
- 238000007654 immersion Methods 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- IQBJFLXHQFMQRP-UHFFFAOYSA-K calcium;zinc;phosphate Chemical compound [Ca+2].[Zn+2].[O-]P([O-])([O-])=O IQBJFLXHQFMQRP-UHFFFAOYSA-K 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- QNNXEUPKHFCUKS-UHFFFAOYSA-J [Ca+2].[Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O Chemical compound [Ca+2].[Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O QNNXEUPKHFCUKS-UHFFFAOYSA-J 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910000398 iron phosphate Inorganic materials 0.000 description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229940114930 potassium stearate Drugs 0.000 description 2
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000005491 wire drawing Methods 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 description 1
- ONMOULMPIIOVTQ-UHFFFAOYSA-N 98-47-5 Chemical class OS(=O)(=O)C1=CC=CC([N+]([O-])=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- TVWHTOUAJSGEKT-UHFFFAOYSA-N chlorine trioxide Chemical compound [O]Cl(=O)=O TVWHTOUAJSGEKT-UHFFFAOYSA-N 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 238000011086 high cleaning Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical class [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- MFXMOUUKFMDYLM-UHFFFAOYSA-L zinc;dihydrogen phosphate Chemical compound [Zn+2].OP(O)([O-])=O.OP(O)([O-])=O MFXMOUUKFMDYLM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/22—Orthophosphates containing alkaline earth metal cations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/367—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing alkaline earth metal cations
Definitions
- the present invention relates to a process for phosphating metal surfaces, and more particularly to zinc-calcium phosphating surfaces of iron, zinc, aluminum, and their alloys as a pretreatment before cold working.
- the process is particularly adapted to phosphating steel.
- Zinc phosphating baths generally contain zinc dihydrogen phosphate, free phosphoric acid, additional zinc salts such as the nitrate, and oxidants (also known as accelerators) as the main components.
- the pH value of such solutions conventionally is in the range between 2.8 and 3.4.
- the process proceeds in two stages, first the dissolution of metal from the surface to be coated as a result of attack on the metal by the acid in the bath and then the formation of a zinc phosphate layer on the surface to be phosphated.
- alkali phosphating processes clean and degrease the metal surface and form an anticorrosive covering layer which mainly consists of iron phosphate.
- the layer formation is initiated by a reaction wherein a small amount of the substrate metal is dissolved.
- the predominant portion of the dissolved surface material reacts with phosphate ions from the solution to form sparingly soluble phosphates which are deposited as a strongly adhering coating on the surface.
- zinc phosphating here the cation in the phosphate layer is derived from the substrate metal itself.
- Iron phosphate layers having a low layer weight of about 0.2 to 0.4 g/m 2
- iron phosphate layers having higher area weights of 0.6 to 1.2 g/m 2 .
- the thin phosphate layers are particularly suitable for being coated with paint; they provide an excellent paint adhesion, good protection from interstitial rust formation, electrical insulation, and reduction in the sliding resistance and facilitate cold working.
- phosphate layers having a layer weight of up to 40 g/m 2 are usually used.
- Metal soaps are known to be formed by the reaction of the known phosphate layers for cold working with appropriate sodium or potassium stearate soaps.
- Aluminum, calcium, lithium, zinc and magnesium stearates are known to be water-repellent and when used as solid lubricants in wire-drawing at higher pressures per unit area provide lower frictional values than those provided by conventional alkali soaps such as sodium stearate.
- European Patent Specification No. 0 045 110 describes a process for the formation of phosphate coatings on iron or steel surfaces by an immersion or flow coating process using an aqueous acidic zinc phosphate solution containing Zn 2+ , PO 4 3- , and NO 3 - or a similarly acting accelerator that does not oxidize iron(II).
- this solution the ratio by weight of Zn:PO 4 is greater than 0.8, the ratio of total acid to free acid is at least 5, and the iron(II) content is adjusted to from 0.05 to 1% by weight by adding a suitable amount of ClO 3 - or another similarly powerful accelerator that oxidizes iron(II) to iron(III).
- Calcium ion is also taught as an optional ingredient in the phosphating solutions used in this reference.
- the present invention is a process for phosphating metal surfaces, and more particularly surfaces of iron, zinc, aluminum, and the alloys thereof as a pretreatment for cold working, wherein the surface is cleaned and/or etched in a conventional manner, except that the metal surfaces without previous activation are contacted in a temperature range of from 30° C. to 70C. with an aqueous solution containing
- the phosphate layer formed has a structure that was not to be expected according to prior art.
- the phosphating solution with which the surfaces to be coated are brought into contact may contain Zn 2+ - and Ca 2+ ions in the ratio by weight of from 1:0.5 to 1:1.5, and preferably in a ratio of 1:1.
- preferred embodiments of the phosphating solutions for use in this invention also contain cations of transition metals in addition to the above-mentioned Ca 2+ and Zn 2+ cations.
- Particularly preferred are Ni 2+ ions
- an amount of from 0.01 to 10 g/l of Ni 2+ ions is preferred.
- phosphating solutions according to the invention may also contain additional anions.
- these anions include simple and/or complex fluorides. These may be used in the phosphating solutions, more preferably, in amounts of from 0.01 to 10 g/l.
- one preferred embodiment of the present invention includes adjusting the temperature range to from 50° C. to 70° C. and contacting the metal surfaces with the phosphating solutions.
- Phosphating solutions for use according to the invention may contain from 0.1 to 2.0 g/l of organic nitro compounds in the place of 10 to 100 g/l NO 3 - - ions.
- Organic nitro compounds within the scope of the present invention are m-nitrobenzene sulfonates and/or nitroguanidine.
- the organic nitro compounds may also be present in an amount of from 0.1 to 2.0 g/l of organic nitro compounds in addition to 10 to 100 g/l NO 3 - - ions in the phosphating solutions.
- the process produces zinc-calcium phosphate (scholzite) layers having an areal mass of from 3 to 9 g/m 2 .
- the zinc-calcium phosphate layers may be produced on the metal surfaces by immersion, spraying and flow coating as well as by combined procedures.
- the surfaces to be phosphated Prior to the application of the phosphating process according to the invention the surfaces to be phosphated are degreased according to processes known in the art. Residues of oil, grease and lubricant or of grinding dust left over from preceding manufacturing processes may be removed by organic solvents or water based cleansing agents.
- Chlorinated hydrocarbons are the most frequently used organic solvents, because they effectively dissolve oils and greases and are not inflammable. However, solid materials and inorganic contaminants on the surface may be insufficiently removed by chlorinated hydrocarbons.
- Water-based cleaning agents have a very high cleaning efficiency. They contain surface-active substances emulsifying oil and grease in water and inorganic components such as carbonates, silicates, borates and phosphates which exhibit alkaline reaction and saponify natural fats.
- a further possibility for pre-cleaning prior to phosphating consists of subjecting the metal surfaces to be cleaned to ultrasonic or mechanical cleaning procedures.
- a major advantage of the present invention is that the zinc-calcium phosphate layers can readily be applied to wire in layer weights of from 3 to 9 g/m 2 .
- the zinc-calcium phosphate layers formed in the process of this invention for the most part contain the mineral scholzite.
- the zinc-calcium phosphate layers Upon reaction of the zinc-calcium phosphate layers with the sodium stearate soaps used in the art, there is formed, in addition to zinc stearate and calcium stearate, a mixed zinc-calcium stearate.
- Zinc-calcium stearate has the advantage in technical wire drawing that the use-life of the drawing die is much increased. Drawing tests in a technical test unit further gave the result that the wire surfaces show a substantially brighter and more uniform optical appearance, especially after a subsequent polishing draw, than is attainable by conventional phosphating procedures run with more highly oxidizing accelerators that readily oxidize iron (ii) to iron (III) in the bath.
- a further advantage of the invention is that the new zinc-calcium phosphating process for cold working may be advantageously performed in a temperature range of from 50° C. to 70° C. Sludging resistance of the solutions is particularly favorable in this process, since even after a bath load of 1.5 m 2 of steel surface per 1 liter of bath solution only a minimum amount of bath sludge, on the order of a few milliliters, is formed.
- a still further advantage of the present invention is that the zinc-calcium stearate mixed soaps that can be formed by reacting the phosphate layers produced by this invention with sodium or potassium stearate enable the drawing die to have a longer use-life.
- a phosphating solution was prepared which contained 10.3 g 1 -1 of Ca 2+ ions, 14.0 g 1 -1 of Zn 2+ ions, 27.8 g 1 -1 of PO 4 3- ions, and 46.5 g 1 -1 of NO 3 - ions. It also had the following characteristics: a pH value of about 2.6, and an acid ratio (free acid to total acid) of about 1:21.
- a solution was prepared which contained 18.0 g/l of Ca 2+ ions, 12.0 g/l of Zn 2+ ions, 2.8 g/l of Ni 2+ ions, 87.2 g/l of PO 4 3- ions, and 27.5 g/l of NO 3 - ions.
- the solution pH value was 2.5, and the ratio of free acid to total acid was 1:17.6.
- the wire thus coated could be readily drawn through several drawing dies in series, to be reduced to a predetermined dimension. In this manner, a bright and shiny surface was formed on the wire.
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- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention relates to a process for phosphating metal surfaces, and more specifically of surfaces of iron, zinc, and aluminum and the alloys thereof as a pretreatment for cold working wherein the surfaces without previous activation are contacted in a temperature range of from 30° C. to 70° C. with an aqueous solution containing
(a) from 10 to 40 g/l of Ca2+ ions,
(b) from 10 to 40 g/l of Zn2+ ions,
(c) from 10 to 100 g/l of OP4 3- ions
and, as accelerator,
(d) from 10 to 100 g/l of NO3 - ions and/or
(e) from 0.1 to 2.0 g/l of organic nitro compounds,
said solution exhibiting a pH value in the range of from 2.0 to 3.8 and a ratio of free acid to total acid of from 1:4 to 1:100.
Description
The present invention relates to a process for phosphating metal surfaces, and more particularly to zinc-calcium phosphating surfaces of iron, zinc, aluminum, and their alloys as a pretreatment before cold working. The process is particularly adapted to phosphating steel.
Processes for phosphating surfaces of iron, steel, zinc and the alloys thereof, and aluminum have long been known. See, e.g., Ullmanns Encyklopadie der technischen Chemie, 4th Edition, Volume 15 Page 686 et seq.). Phosphating said surfaces serves to increase the adhesion strength of subsequently applied paint or similar surface finishing materials and to improve the protection from corrosion.
The two most important general types of phosphating processes are zinc phosphating and alkali phosphating. Zinc phosphating baths generally contain zinc dihydrogen phosphate, free phosphoric acid, additional zinc salts such as the nitrate, and oxidants (also known as accelerators) as the main components. The pH value of such solutions conventionally is in the range between 2.8 and 3.4. The process proceeds in two stages, first the dissolution of metal from the surface to be coated as a result of attack on the metal by the acid in the bath and then the formation of a zinc phosphate layer on the surface to be phosphated.
In contrast, alkali phosphating processes clean and degrease the metal surface and form an anticorrosive covering layer which mainly consists of iron phosphate. The layer formation is initiated by a reaction wherein a small amount of the substrate metal is dissolved. The predominant portion of the dissolved surface material reacts with phosphate ions from the solution to form sparingly soluble phosphates which are deposited as a strongly adhering coating on the surface. In contrast to zinc phosphating, here the cation in the phosphate layer is derived from the substrate metal itself.
In anticorrosion alkali phosphating, there are two common layer types: Iron phosphate layers having a low layer weight of about 0.2 to 0.4 g/m2, and iron phosphate layers having higher area weights of 0.6 to 1.2 g/m2. The thin phosphate layers are particularly suitable for being coated with paint; they provide an excellent paint adhesion, good protection from interstitial rust formation, electrical insulation, and reduction in the sliding resistance and facilitate cold working.
In order to form smooth phosphate layers, it is usually advantageous to "activate" the surfaces by contact with a solution containing a suitable form of soluble titanium before contacting the surfaces with the phosphating bath. For some types of baths, however, such activation is not needed.
For cold working, phosphate layers having a layer weight of up to 40 g/m2 are usually used. Metal soaps are known to be formed by the reaction of the known phosphate layers for cold working with appropriate sodium or potassium stearate soaps. Aluminum, calcium, lithium, zinc and magnesium stearates are known to be water-repellent and when used as solid lubricants in wire-drawing at higher pressures per unit area provide lower frictional values than those provided by conventional alkali soaps such as sodium stearate.
Since the melting points of these other metal stearates are lower than those of sodium stearate, and the other metal stearates when used alone are too oily, in practice supporting materials such as lime are usually incorporated in order to retain the other metal soaps in the drawing zone where lubricant is needed. Other metal soaps have the advantages over alkali soaps that they absorb hardly any moisture from the air, retain their lubricating power unchanged due to their high compression stability, and enable higher reductions in cross section to be employed, whereas the lubricating effect of alkali soaps may be greatly lowered by moisture absorption.
European Patent Specification No. 0 045 110 describes a process for the formation of phosphate coatings on iron or steel surfaces by an immersion or flow coating process using an aqueous acidic zinc phosphate solution containing Zn2+, PO4 3-, and NO3 - or a similarly acting accelerator that does not oxidize iron(II). In this solution the ratio by weight of Zn:PO4 is greater than 0.8, the ratio of total acid to free acid is at least 5, and the iron(II) content is adjusted to from 0.05 to 1% by weight by adding a suitable amount of ClO3 - or another similarly powerful accelerator that oxidizes iron(II) to iron(III). Calcium ion is also taught as an optional ingredient in the phosphating solutions used in this reference.
It is an object of the present invention to provide an improved process for phosphating metal surfaces, and more specifically, surfaces of iron, zinc, aluminum and the alloys thereof as a pretreatment for cold working.
Except in the operating examples, or where otherwise specifically indicated, all numbers in this description that specify amounts of ingredients or reaction conditions are to be understood as modified by the word "about".
In brief, the present invention is a process for phosphating metal surfaces, and more particularly surfaces of iron, zinc, aluminum, and the alloys thereof as a pretreatment for cold working, wherein the surface is cleaned and/or etched in a conventional manner, except that the metal surfaces without previous activation are contacted in a temperature range of from 30° C. to 70C. with an aqueous solution containing
(a) from 10 to 40 g/l of Ca2+ ions,
(b) from 10 to 40 g/l of Zn2+ ions,
(c) from 10 to 100 g/l of PO4 3- ions
and, as accelerator,
(d) from 10 to 100 g/l of NO3 - ions and/or
(e) from 0.1 to 2.0 g/l of organic nitro compounds, said solution exhibiting a pH value in the range of from 2.0 to 3.8 and a ratio of free acid to total acid of from 1:4 to 1:100.
Surprisingly, although the Zn:Ca ratio is different from that preferred according to the European Patent 0 045 101 and in spite of the high proportions of calcium in the phosphating solution, the phosphate layer formed has a structure that was not to be expected according to prior art.
According to a preferred embodiment of the present invention, the phosphating solution with which the surfaces to be coated are brought into contact may contain Zn2+ - and Ca2+ ions in the ratio by weight of from 1:0.5 to 1:1.5, and preferably in a ratio of 1:1.
Advantageously, preferred embodiments of the phosphating solutions for use in this invention also contain cations of transition metals in addition to the above-mentioned Ca2+ and Zn2+ cations. Particularly preferred are Ni2+ ions When the phosphating solutions contain Ni2+ ions, an amount of from 0.01 to 10 g/l of Ni2+ ions is preferred.
In addition to the anions mentioned such as PO4 3- and NO3 - ions, phosphating solutions according to the invention may also contain additional anions. According to one preferred embodiment, these anions include simple and/or complex fluorides. These may be used in the phosphating solutions, more preferably, in amounts of from 0.01 to 10 g/l.
While the process according to the invention is regularly carried out in the range of from 30° C. to 70° C., one preferred embodiment of the present invention includes adjusting the temperature range to from 50° C. to 70° C. and contacting the metal surfaces with the phosphating solutions.
Phosphating solutions for use according to the invention may contain from 0.1 to 2.0 g/l of organic nitro compounds in the place of 10 to 100 g/l NO3 - - ions. Organic nitro compounds within the scope of the present invention are m-nitrobenzene sulfonates and/or nitroguanidine. The organic nitro compounds may also be present in an amount of from 0.1 to 2.0 g/l of organic nitro compounds in addition to 10 to 100 g/l NO3 - - ions in the phosphating solutions. According to one preferred embodiment of the present invention, the process produces zinc-calcium phosphate (scholzite) layers having an areal mass of from 3 to 9 g/m2.
The zinc-calcium phosphate layers may be produced on the metal surfaces by immersion, spraying and flow coating as well as by combined procedures. Prior to the application of the phosphating process according to the invention the surfaces to be phosphated are degreased according to processes known in the art. Residues of oil, grease and lubricant or of grinding dust left over from preceding manufacturing processes may be removed by organic solvents or water based cleansing agents.
Chlorinated hydrocarbons are the most frequently used organic solvents, because they effectively dissolve oils and greases and are not inflammable. However, solid materials and inorganic contaminants on the surface may be insufficiently removed by chlorinated hydrocarbons. Water-based cleaning agents have a very high cleaning efficiency. They contain surface-active substances emulsifying oil and grease in water and inorganic components such as carbonates, silicates, borates and phosphates which exhibit alkaline reaction and saponify natural fats.
A further possibility for pre-cleaning prior to phosphating consists of subjecting the metal surfaces to be cleaned to ultrasonic or mechanical cleaning procedures.
A major advantage of the present invention is that the zinc-calcium phosphate layers can readily be applied to wire in layer weights of from 3 to 9 g/m2.
The zinc-calcium phosphate layers formed in the process of this invention for the most part contain the mineral scholzite. Upon reaction of the zinc-calcium phosphate layers with the sodium stearate soaps used in the art, there is formed, in addition to zinc stearate and calcium stearate, a mixed zinc-calcium stearate.
Zinc-calcium stearate has the advantage in technical wire drawing that the use-life of the drawing die is much increased. Drawing tests in a technical test unit further gave the result that the wire surfaces show a substantially brighter and more uniform optical appearance, especially after a subsequent polishing draw, than is attainable by conventional phosphating procedures run with more highly oxidizing accelerators that readily oxidize iron (ii) to iron (III) in the bath.
A further advantage of the invention is that the new zinc-calcium phosphating process for cold working may be advantageously performed in a temperature range of from 50° C. to 70° C. Sludging resistance of the solutions is particularly favorable in this process, since even after a bath load of 1.5 m2 of steel surface per 1 liter of bath solution only a minimum amount of bath sludge, on the order of a few milliliters, is formed. A still further advantage of the present invention is that the zinc-calcium stearate mixed soaps that can be formed by reacting the phosphate layers produced by this invention with sodium or potassium stearate enable the drawing die to have a longer use-life.
The practice of the invention is illustrated by the following operating examples, which are not intended to limit the invention in any way.
A phosphating solution was prepared which contained 10.3 g 1-1 of Ca2+ ions, 14.0 g 1-1 of Zn2+ ions, 27.8 g 1-1 of PO4 3- ions, and 46.5 g 1-1 of NO3 - ions. It also had the following characteristics: a pH value of about 2.6, and an acid ratio (free acid to total acid) of about 1:21.
Steel wires which previously had been cleaned with an alkaline cleansing solution by an immersion treatment at 80° C. for 10 minutes and rinsed with water were treated with the above phosphating solution by immersion at 50° C. for 7 min. Then the wires were rinsed with water, and a reactive soap was applied to the wire surface. Then the wires were drawn through drawing dies. The result was a very bright and shiny surface, which could not be attained by using phosphating solutions other than those according to the invention.
A solution was prepared which contained 18.0 g/l of Ca2+ ions, 12.0 g/l of Zn2+ ions, 2.8 g/l of Ni2+ ions, 87.2 g/l of PO4 3- ions, and 27.5 g/l of NO3 - ions. The solution pH value was 2.5, and the ratio of free acid to total acid was 1:17.6.
Steel wire which previously had been cleaned in an alkaline immersion bath at 80° C. for 10 minutes and then cold rinsed was treated with the above phosphating solution by immersion at 55° C. for 10 min. Then the wires were rinsed with water, and a reactive drawing soap was applied to the wire in an immersion bath at 80° C.
The wire thus coated could be readily drawn through several drawing dies in series, to be reduced to a predetermined dimension. In this manner, a bright and shiny surface was formed on the wire.
Claims (16)
1. In a process comprising cleaning and phosphating metal surfaces, the improvement wherein the surfaces without previous activation are contacted in a temperature range of from 30° C. to 70° C. with an aqueous solution consisting essentially of:
(a) from about 10 to about 40 g/l of Ca2+ ions,
(b) from about 10 to about 40 g/l of Zn2+ ions,
(c) from about 10 to about 100 g/l of PO4 3- ions,
(d) an accelerator selected from the group consisting of
(i) about 10 to about 100 g/l of nitrate ions and
(ii) about 0.1 to about 2.0 g/l of organic nitro compounds,
(e) up to about 10 g/l of Ni2+ ions, and
(f) up to abut 10 g/l of simple, complex, or mixed simple and complex fluoride ions,
said solution having a pH value in the range from about 2.0 to about 3.8, a ratio of free acid to total acid from about 1:4 to 1:100, and a ratio by weight of Zn+2 ions to Ca+2 ions of about 1:0.5 to about 1:1.5; said process producing on the metal surfaces a phosphate layer containing scholzite in an areal density between about 3 and about 9 g/m2.
2. A process according to claim 1, wherein the phosphating solution comprises Ni2+ ions in an amount of at least about 0.01 g/l.
3. A process according to claim 2, wherein the phosphating solution comprises simple, complex, or mixed simple and complex fluoride ions in an amount of at least about 0.01 g/l.
4. A process according to claim 3, characterized in that the metal surfaces are phosphated at temperatures between about 50° C. and about 70° C.
5. A process according to claim 2, characterized in that the metal surfaces are phosphated at temperatures between about 50° C. and about 70° C.
6. A process according to claim 1, characterized in that the metal surfaces are phosphated at temperatures between about 50° C. and about 70° C.
7. A process according to claim 6, wherein the metal phosphated is an alloy of iron, zinc, or aluminum.
8. A process according to claim 5, wherein the metal phosphated is an alloy of iron, zinc, or aluminum.
9. A process according to claim 4, wherein the metal phosphated is an alloy of iron, zinc, or aluminum.
10. A process according to claim 3, wherein the metal phosphated is an alloy of iron, zinc or aluminum.
11. A process according to claim 2, wherein the metal phosphated is an alloy of iron, zinc or aluminum.
12. A process according to claim 1, wherein the metal phosphated is an alloy of iron, zinc, or aluminum.
13. A process according to claim 12, additionally comprising cold working the phosphated metal surfaces after reacting these surfaces with an alkali stearate to produce a mixed calcium-zinc stearate on the surfaces.
14. A process according to claim 6, additionally comprising cold working the phosphated metal surfaces after reacting these surfaces with an alkali stearate to produce a mixed calcium-zinc stearate on the surfaces.
15. A process according to claim 3, additionally comprising cold working the phosphated metal surfaces after reacting these surfaces with an alkali stearate to produce a mixed calcium-zinc stearate on the surfaces.
16. A process according to claim 1, additionally comprising cold working the phosphated metal surfaces after reacting these surfaces with an alkali stearate to produce a mixed calcium-zinc stearate on the surfaces.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3800835 | 1988-01-14 | ||
| DE3800835A DE3800835A1 (en) | 1988-01-14 | 1988-01-14 | METHOD FOR PHOSPHATING METAL SURFACES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4944813A true US4944813A (en) | 1990-07-31 |
Family
ID=6345237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/297,155 Expired - Fee Related US4944813A (en) | 1988-01-14 | 1989-01-13 | Process for phosphating metal surfaces |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4944813A (en) |
| EP (1) | EP0324395B1 (en) |
| JP (1) | JPH01219172A (en) |
| AT (1) | ATE83509T1 (en) |
| AU (1) | AU604395B2 (en) |
| BR (1) | BR8900148A (en) |
| DE (2) | DE3800835A1 (en) |
| MX (1) | MX169762B (en) |
| TR (1) | TR26644A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5236519A (en) * | 1990-01-18 | 1993-08-17 | Nihon Parkerizing Co., Ltd. | Method for lubricating treatment of aluminum |
| US5264254A (en) * | 1990-09-21 | 1993-11-23 | Tegometall Rudolf Bohnacker | Powder coating method for metallic surfaces |
| US5344713A (en) * | 1989-04-03 | 1994-09-06 | Sumitomo Electric Industries Ltd. | Method for manufacturing steel wire material for reinforcing optical fiber |
| US5968240A (en) * | 1997-08-19 | 1999-10-19 | Sermatech International Inc. | Phosphate bonding composition |
| RU2160324C1 (en) * | 1999-03-11 | 2000-12-10 | Закрытое акционерное общество "Мультисервис" | Composition for protection from corrosion of ferrous metal surfaces |
| US6231687B1 (en) * | 1998-10-07 | 2001-05-15 | Henkel Corporation | Lubrication treatment method for cold working of steel |
| RU2174161C1 (en) * | 2000-10-30 | 2001-09-27 | Танасиенко Сергей Юрьевич | Anticorrosive composition and method of its application to metal surface |
| US6902766B1 (en) | 2000-07-27 | 2005-06-07 | Lord Corporation | Two-part aqueous metal protection treatment |
| US20060278307A1 (en) * | 2003-05-23 | 2006-12-14 | Thomas Nitschke | Method and solution for coating metal surfaces with a posphating solution containing water peroxide, produced metal object and use of said object |
| US20070051156A1 (en) * | 2005-08-31 | 2007-03-08 | Aisin Aw Co., Ltd. | Manufacturing method for an annular member and a pronged annular member |
| CN101189366A (en) * | 2005-05-19 | 2008-05-28 | 凯密特尔有限责任公司 | Method for preparing a metal workpiece for cold forming |
| US20110198000A1 (en) * | 2002-07-10 | 2011-08-18 | Specht Juergen | Process for coating metallic surfaces |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19634685A1 (en) * | 1996-08-28 | 1998-03-05 | Metallgesellschaft Ag | Aqueous solution and process for phosphating metallic surfaces |
| DE19808440C2 (en) | 1998-02-27 | 2000-08-24 | Metallgesellschaft Ag | Aqueous solution and method for phosphating metallic surfaces and use of the solution and method |
| DE10320313B4 (en) * | 2003-05-06 | 2005-08-11 | Chemetall Gmbh | A method of coating metallic bodies with a phosphating solution, phosphating solution and the use of the coated article |
| JP5153063B2 (en) * | 2005-07-15 | 2013-02-27 | 日本発條株式会社 | Steel surface treatment method |
| JP6879090B2 (en) * | 2017-07-07 | 2021-06-02 | 三菱瓦斯化学株式会社 | Method for manufacturing rolls and sheet molded products for melt extrusion |
| EP4121580A1 (en) * | 2020-03-19 | 2023-01-25 | ThyssenKrupp Steel Europe AG | Method for generating a phosphate conversion coating and nickel-free phosphating solution |
| EP3964606A1 (en) * | 2020-09-04 | 2022-03-09 | Henkel AG & Co. KGaA | Single stage zinc phosphating method |
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- 1988-01-14 DE DE3800835A patent/DE3800835A1/en not_active Withdrawn
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- 1989-01-07 DE DE8989100228T patent/DE58902980D1/en not_active Expired - Fee Related
- 1989-01-07 AT AT89100228T patent/ATE83509T1/en not_active IP Right Cessation
- 1989-01-12 TR TR89/0045A patent/TR26644A/en unknown
- 1989-01-13 US US07/297,155 patent/US4944813A/en not_active Expired - Fee Related
- 1989-01-13 BR BR898900148A patent/BR8900148A/en unknown
- 1989-01-13 AU AU28508/89A patent/AU604395B2/en not_active Ceased
- 1989-01-13 MX MX014531A patent/MX169762B/en unknown
- 1989-01-17 JP JP1009621A patent/JPH01219172A/en active Pending
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5344713A (en) * | 1989-04-03 | 1994-09-06 | Sumitomo Electric Industries Ltd. | Method for manufacturing steel wire material for reinforcing optical fiber |
| US5236519A (en) * | 1990-01-18 | 1993-08-17 | Nihon Parkerizing Co., Ltd. | Method for lubricating treatment of aluminum |
| US5264254A (en) * | 1990-09-21 | 1993-11-23 | Tegometall Rudolf Bohnacker | Powder coating method for metallic surfaces |
| US5968240A (en) * | 1997-08-19 | 1999-10-19 | Sermatech International Inc. | Phosphate bonding composition |
| US6231687B1 (en) * | 1998-10-07 | 2001-05-15 | Henkel Corporation | Lubrication treatment method for cold working of steel |
| RU2160324C1 (en) * | 1999-03-11 | 2000-12-10 | Закрытое акционерное общество "Мультисервис" | Composition for protection from corrosion of ferrous metal surfaces |
| US6902766B1 (en) | 2000-07-27 | 2005-06-07 | Lord Corporation | Two-part aqueous metal protection treatment |
| RU2174161C1 (en) * | 2000-10-30 | 2001-09-27 | Танасиенко Сергей Юрьевич | Anticorrosive composition and method of its application to metal surface |
| US20110198000A1 (en) * | 2002-07-10 | 2011-08-18 | Specht Juergen | Process for coating metallic surfaces |
| US8349092B2 (en) | 2002-07-10 | 2013-01-08 | Chemetall Gmbh | Process for coating metallic surfaces |
| US20060278307A1 (en) * | 2003-05-23 | 2006-12-14 | Thomas Nitschke | Method and solution for coating metal surfaces with a posphating solution containing water peroxide, produced metal object and use of said object |
| US20110180186A1 (en) * | 2003-05-23 | 2011-07-28 | Thomas Nitschke | Method and solution for coating metallic surfaces with a phosphating solution containing hydrogen peroxide, metallic object produced and use of the object |
| US20080166575A1 (en) * | 2005-05-19 | 2008-07-10 | Chemetall Gmbh | Method For Preparing Metallic Workplaces For Cold Forming |
| CN101189366A (en) * | 2005-05-19 | 2008-05-28 | 凯密特尔有限责任公司 | Method for preparing a metal workpiece for cold forming |
| CN101189366B (en) * | 2005-05-19 | 2015-05-06 | 凯密特尔有限责任公司 | Method for preparing metallic workpieces for cold forming |
| US20070051156A1 (en) * | 2005-08-31 | 2007-03-08 | Aisin Aw Co., Ltd. | Manufacturing method for an annular member and a pronged annular member |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE83509T1 (en) | 1993-01-15 |
| AU2850889A (en) | 1989-07-20 |
| DE3800835A1 (en) | 1989-07-27 |
| JPH01219172A (en) | 1989-09-01 |
| MX169762B (en) | 1993-07-23 |
| EP0324395A1 (en) | 1989-07-19 |
| EP0324395B1 (en) | 1992-12-16 |
| DE58902980D1 (en) | 1993-01-28 |
| TR26644A (en) | 1994-05-25 |
| BR8900148A (en) | 1989-09-12 |
| AU604395B2 (en) | 1990-12-13 |
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